Herbicidal n-octahydro-1,2,4-methenopentalenyl-(5)-ureas

ABSTRACT

HERBICIDAL COMPOUNDS OF THE FORMULA   5-(R1-N(-R2)-CO-NH-)OCTAHYDRO-1,2,4-METHENOPENTALENE   IN WHICH   R1 REPRESENTS HYDROGEN, LOWER ALIPHATIC HYDROCARBONS CYCLOALKYL, LOWER ALKOXY, OR PHENYL, R2 REPRESENTS HYDROGEN, LOWER ALKYL, OR LOWER ALKENYL, OR R1 AND R2 TOGETHER REPRESENT ETHYLENEOXYETHYLENE OR A POLYMETHYLENE BRIDGING MEMBER. ARE DESCRIBED AS PARTICULARLY SUITABLE FOR CONTROLLING WEEDS AND UNDESIRABLE GRASSES. COMPOSITIONS CONTAINING THESE COMPOUNDS AS ACTIVE INGREDIENTS IN MIXTURE WITH AGRICULTURALLY ACCEPTABLE CARRIRS AND A METHOD OF CONTROLLING WEEDS AND UNDESIRABLE GRASSES WITH THE AID OF SUCH COMPOUNDS OR COMPOSITIONS CONTAINING THEM ARE ALSO DESCRIBED, AS WELL AS INTERMEDIATES WHICH ARE METHENOPENTALENE DERIVATIVES FROM WHICH THE COMPOUNDS OF THE ABOVE FORMULA CAN BE PRODUCED.

United States Patent U.S. Cl. 260553 Claims ABSTRACT OF THE DISCLOSUREHerbicidal compounds of the formula R represents hydrogen, loweraliphatic hydrocarbons, cy-

. cloalkyl, lower alkoxy, or phenyl,

R represents hydrogen, lower alkyl, or lower alkenyl, or

R and R together represent ethyleneoxyethylene or a polymethylenebridging member.

in which are described as particularly suitable for controlling weedsand undesirable grasses. Compositions containing these compounds asactive ingredients in mixture with agriculturally acceptable carriersand a method of controlling weeds and undesirable grasses with the aidof such compounds or compositions containing them are also described, aswell as intermediates which are methenopentalene derivatives from whichthe compounds of the above formula can be produced.

The present invention concerns new ureas, processes for the productionthereof and new methenopentalene derivatives serving as startingmaterials therefor, herbicidal compositions which contain the new ureasas active ingredients, and a method for controlling undesirable plantgrowth with the aid of the new ureas or compositions containing the sameas active ingredients.

It has been found that new urea derivatives of the formula wherein Rrepresents hydrogen, a lower aliphatic hydrocarbon radical, a cycloalkylradical, a lower alkoxy radical or the phenyl radical,

R represents hydrogen, a lower alkyl or a lower alkenyl radical, or

R and R together represent the ethylenoxyethylene radical or apolymethylene bridging member,

have excellent herbicidal properties and are valuable for controllingweeds and undesirable grasses. The active substances can be used in thepre-emergence as well. as in the post-emergence treatment for thecontrol of undesirable plant growth in cultivated crops. They aredistinguished in particular by their quick onset of action as well asshort-time residual effects.

' In the urea derivatives of general Formula I, R as lower aliphatichydrocarbon radical, can represent a lower Patented Jan. 12, 1971 icealkyl radical having 1 to 5 carbon atoms such as the methyl, ethyl,propyl, butyl or amyl radicals, etc., a lower alkenyl radical such asthe allyl or methallyl radical, or it can be an alkinyl radical such asthe propinyl or 1-methyl-2-propinyl radical; as cycloalkyl radical, ithas preferably from 3 to 8 carbon atoms and can, for instance, be acyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclooctyl radical;as alkoxy radical it can be, e.g., the methoxy, ethoxy, propoxy orbutoxy radicals. As lower alkyl radical, the symbol R can be one ofthose radicals mentioned above for R The polymethylene bridging membersymbolised by R and R together has from 3 to 6 chain members and is,e.g., the trimethylene, tetramethylene, pentamethylene or hexamethylenegroup.

The new ureas of Formula I are obtained by reacting a functionalderivative of octahydro-1,2,4-methenopentalenyl-(5)-carbamic acid withan amine of general Formula II R2 (II) wherein R and R have the meaningsgiven in Formula I, in the presence of a solvent which is inert to thereaction components.

According to another analogous process, the ureas of general Formula Iare obtained by reacting octahydro- 1,2,4-methenopentalenyl-(5)-aminewith either:

(a) A carbamic acid halide of the general Formula III wherein Halrepresents halogen up to the atomic number 35,

R represents hydrogen, a lower aliphatic hydrocarbon radical, acycloalkyl radical, a lower alkoxy radical or the phenyl radical,

R represents hydrogen or a lower alkyl radical, or

R and R together represent the ethyleneoxyethylene radical or apolymethylene bridging member, or

(b) The components for the formation of such a carbamic acid halide ofFormula III, i.e., with phosgene and an amine of Formula II, in thepresence of a condensing agent, and, preferably, in a solvent or diluentwhich is inert to the reaction components.

The octahydro-pentalenyl-(S)-ureas of the general Formula I wherein R isa lower aliphatic hydrocarbon radical, a cycloalkyl radical or thephenyl radical and R is hydrogen, are also obtained according to theinvention by reacting octahydro-1,2,4-methen0pentalenyl (5) amine withan isocyanate of the general Formula IV R NCO (IV) wherein 1 Rrepresents a lower aliphatic hydrocarbon radical, a

cycloalkyl radical or the phenyl radical.

Reactive functional derivatives of the carbamic acid mentioned are, forexample, the following: the isocyanate, the lower alkyl esters,particularly the methyl or ethyl ester, also the phenyl ester, as Wellas monoand disubstituted amides.

The new ureas of the general Formula I wherein R is a lower alkoxyradical, can be produced by subsequent alkylation, in the presence of anacid binding agent, of an N octahydro 1,2,4methenopentalenyl-(S)-N-alkoxy urea or of anN-octahydro-1,2,4-methenopentalenyl-(5 N'-hydroxy urea with the usualalkylating agents such as alkyl halides, dialkyl sulphates, etc. TheN-octahydro- 1,2,4-methenopentalenyl-(5)-N'-alkoxy ureas can be obtainedin their turn by reaction of the octahydro-1,2,4-methenopentalenyl-(S)-isocyanate with an O-alkyl hydroxylamino [0.Scherer et al., Angnew. Chemie, 75, 851854 (1963)].

Examples of inert solvents suitable for the modifications mentioned ofthe process according to the invention are hydrocarbons such as benzene,toluene, xylenes; ethers such as diethyl ether, dioxane,tetrahydrofuran, diethylene glycol monomethyl ether; chlorinatedhydrocarbons such as methylene chloride, and low ketones such as acetoneor methylethyl ketone.

The reaction of the isocyanate, of a carbamic acid ester or amide (urea)is generally performed without condensing agent. In some cases it can beof advantage to perform the reaction in the presence of, e.-g., alkalimetal alcoholates or a tertiary organic base.

The reaction of octahydro-l,2,4-methenopentalenyl- (5)-amine with acarbamoyl halide or components for the formation of same (phosgene/amineof Formula II) is performed in the presence of a condensing agent suchas an inorganic base, e.g., alkali metal hydroxide or acetate, hydrogencarbonate, carbonate and phosphate, or in the presence of an organicbase, e.g., a tertiary amine such as pyridine, trialkylamine orcollidine. Amines of the general Formula II which are useful are, e.g.,the following: methylamine, dimethylamine, ethylamine, diethylamine, thepropylamines and the butylamines, cyclopropylamine, cyclobutylamine,cyclopentylamine, cyclohexylamine, also aniline, acetidine, pyrrolidine,piperidine and morpholine. These amines can be used in the reaction bothin the free form and also as salts of hydrohalic acids, preferably ashydrochlorides.

As isocyanates of general Formula IV, the corresponding alkylisocyanates can be used such as the methyl, ethyl and propylisocyanates, phenyl isocyanate, the allyl isocyanate, also thecyclopropyl, cyclobutyl, and cyclohexyl isocyanate. As carbamic acidhalides of Formula III, particularly the dialkyl and alkylaryl carbamicacid chlorides and bromides such as dimethyl, diethyl, di-isopropyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and methylphenylcarbamic acid chloride, can be reacted according to the presentinvention.

Both octahydro-l,2,4-methenpentalenyl-(5 )-isocyanate andoctahydro-1,2,4-methenopentalenyl-()-amine have not been known hitherto.These compounds, which serve as intermediate products, are obtained bydegrading functional reactive derivatives ofoctahydro-1,2,4-methenopentalenyl-(S)-carboxylic acid. The azide andamide can be used as reactive functional derivatives which are degradedaccording to Curtius or Hofmann to the isocyanate and aminerespectively.

The starting isocyanate is produced, preferably, by Curtius degradationof the azide. For this purpose, either the carboxylic acid chloridewhich is then reacted with alkali metal azide to form the desiredcarboxylic acid azide; or one of the alkyl esters such the methyl orethyl ester is converted into the carboxylic acid azide direct withhydrazine hydrate and nitrous acid, preferably in the presence of asolvent or diluent. The azide is converted into the isocyanate bythermic decomposition in a solvent which is inert to the reactioncomponents such as in an aromatic hydrocarbon such as benzene, toluene,xylenes, or in a higher boiling ether such as dioxane. The temperaturefor the decomposition of the azide lies between 20 and 180 C.

The isocyanate is converted into the octahydro-1,2,4-methenopentalenyl-(S)-amine by reacting it either with (a) glacialacetic acid and acetic acid anhydride, or (b) with an alkanol. In theformer case (a), the acetylamine is obtained as reaction product whichis converted into the free amine by alkaline saponification. In case(b), the carbamic acid esters corresponding to the alkanols used areobtained which can be converted by acid as well as basic hydrolysis intothe amine mentioned. Hydrohalic acids,

4 glacial acetic acid, halogenated acetic acids or mixtures of suchacids, e.g., can be used for acid hydrolysis; alkali metal and alkalineearth metal hydroxides, for example, are suitable for basic hydrolysis.The hydrolysis can be performed both in water as well as in an alkanolsuch as methanol and ethanol or in diethylene glycol, etc.

In addition, octahydro-l,2,4-methenopentalenyl-(5)- amine can beobtained by acid amide degradation according to Holmann. For thispurpose, the corresponding carboxylic acid amide is heated, e.g., in thepresence of an agent giving off bromine or chlorine, the presence of analkali metal or alkaline earth metal hydroxide or an acid. Both water aswell as an alkanol are suitable as solvent, but in cases where thedegradation is performed in an alkanol, e.g., methanol or ethanol thecorresponding alcoholates are used instead of the hydroxides mentioned.

The new ureas of the general Formula I, in the purified state, arecolourless and dissolve well in organic solvents; on the other hand,they are insoluble in water.

Compounds according to the invention are particularly useful in theselective control of weeds and other undesirable plant growth incultivated crops. The amounts required per hectare range from about 0.25to preferably not more than 5 kg.

For instance, N dimethyl N [octahydro 1,2,4- methenopentalenyl-(S -ureais particularly recommended for use in the post-emergence weed controlin corn or bean crops. Pastinaca, rye grass and vetch are destroyed,when the herbicide is applied in concentrations of about 0.5 to 3 kg.per hectare, while the corn or beans remain practically unaffected.

N diethyl N [octahydro-1,2,4-methenopentalenyl- (5)]-urea is anexcellent herbicide for the selective control of weeds and grasses,e.g., rye grass, in beans, millet, corn, flax and sunflower crops.

When applied in pre-emergence treatment, about 0.5 to 3 kg. per hectareof this compound are adequate for weed control, while in post-emergencetreatments larger amounts of up to 5 kg. per hectare may be requireddepending on the climatic and soil conditions and on the crop to beprotected.

Good weed control was also achieved against dicotyle weeds inpre-emergence tests in summer wheat and sugar beet fields and inpost-emergence tests in summer wheat, as well as against such weeds as Apera spica and Matricaria in winter wheat.

N methoxy-N -methyl-N -[octahydro-l,2,4-methenopentalenyl-(5)]-urea isparticularly suited for controlling undesirable growth of grasses of allkinds in corn and sunflower crops and, in post-emergence treatment, alsoin millet.

Particularly good herbicidal activity of this compound was found intests in summer wheat, rye and barley crops when applying the compoundin amounts of from about 0.25 to preferably not more than 1 kg. perhectare, especially in a post-emergence treatment.

Particularly preferred because of very satisfactory herbicidal activityare those compounds of Formula I in which R represents hydrogen, alkylof from 1 to 5 carbon atoms, alkenyl of from 3 to 4 carbon atoms,alkinyl of from 3 to 4 carbon atoms, cycloalkyl of from 3 to 6 carbonatoms, alkoxy of from 1 to 4 carbon atoms, or phenyl;

R represents hydrgen, alkyl of from 1 to 5 carbon atoms or alkenyl offrom 3 to 4 carbon atoms, or

R and R together with the nitrogen atom to which they are linkedrepresent an acetidino, pyrrolidino, piperidino, hexahydroazepino ormorpholino group.

Those compounds of Formula I in which both R and R represent hydrogen,or one represents hydrogen and the other methyl, or both representmethyl, or both ethyl, or both together represent tetramethylcne, orpentamethylene, or ethylene-oxy-ethylene, or R represents methyl and Reither 1-methyl-2-propinyl or methoxy have proven particularly valuablein the control of weeds and undesirable grasses.

Parts and percentages mentioned in this specification and in theappended claims are given by weight unless expressly stated otherwise.

Concentrations of active ingredient in solid mixtures are given inpercent of the total weight of the mixture, and in substantially liquidpreparations they are given by percent weight of active substance pertotal volume of the preparations. The relationship of parts by weight toparts by volume is that of kilograms to liters.-

The following nonlimitative examples illustrate the invention further.The temperatures are given therein in degrees centigrade.

EXAMPLE 1 (1) Production of the starting material (a) 164 parts of theknown octahydro-1,2,4-methenopentalenyl-(S)-carboxylic acid [cf. H. K.Hall, J. Org. Chem. 25, 42 (1960)], 1000 parts by volume of benzene and4 parts by volume of pyridine are gently heated on a steam bath. 250parts of thionyl chloride are added dropwise within 15 minutes in such away that the reaction proceeds by itself with S development. Oncompletion of the addition of the thionyl chloride, the whole is heatedfor another 15 minutes on the steam bath, after which all volatileproducts are removed at room temperature by water jet vacuum. 200 partsby volume of petroleum ether are added to the residue, the mixture isleft to stand for 30 minutes and then filtered. The solvent is removedin the evaporator. The octahydro-1,2,4-methenopentalenyl-(S)-carboxylicacid chloride obtained is distilled; it boils at 6365/ 2 torr. (Yield:162.7 parts; 88.5%.)

(b) 93.6 parts of sodium azide are dissolved in 1720 parts by volume of50% aqueous acetone and the solution is cooled to 0. 90 parts of theoctahydro-1,2,4-methenopentalenyl-()-carboxylic acid chloride obtainedaccording to (a) are then added within 5-10 minutes. The temperature inthe reaction vessel is kept at 02 by exterior cooling. On completion ofthe addition, the whole is stirred at 0 for another 50 minutes, afterwhich the solution is extracted, first with 1000 parts by volume of icecold benzene and then a second time with 300 parts by volume of ice coldbenzene. The combined benzene extracts are then dried with finelypulverised calcium chloride at 0-5. The calcium chloride is filteredofi? and the filtrate is heated for 2 /2 hours in a steam bath. Nitrogenis developed and the solution foams. The benzene is then distilled off.The octahydro-1,2,4-methenopentalenyl- (5)-isocyanate'boils at 70-75/3torr.

(2) Production of a urea derivative according to the invention (0) 16.1parts of octahydro-l,2,4-methenopentalenyl (5)-isocyanate (cf. Example1(b)) in 200 parts by volume of benzene are reacted with 9.7 parts ofdiethylamine. After removal of the solvent, the crude product isdistilled: B.P. 131134/0.004 torr. After recrystallisation frompetroleum ether, N-octahydro-1,2,4-methenopentalenyl-(5)-N',N'-diethylurea is obtained as colourless crystals.

EXAMPLE 2 (a) 16.1 parts of octahydro-1,2,4-methenopentalenyl-(5)-isocyanate (cf. Example 1(b)) are boiled for 100 minutes in amixture of 25 parts by volume of glacial acetic acid and parts by volumeof acetic acid anhydride. On completion of the CO development, 35 partsby volume of the solvent are distilled ofl? and the residue is pouredinto 100 parts by volume of water and then stirred for 3 hours. Theprecipitated crystalline product is taken up in 175 parts by volume ofether, the ethereal solu tion is washed with 15 parts by volume of waterand dried with sodium sulphate. After removal of the ether, the

residue is distilled. Theoctahydro-1,2,4-methenopentalenyl-(5)-acetylamine obtained boils at120-125/ 0.05 torr, and melts at 7780.

(b) 26.5 parts of the acetyl amine obtained above are boiled in asolution of 200 parts by volume of diethylene glycol monomethyl etherand 42 parts of potassium hydroxide in 50 parts by volume of water. 35parts by volume of water are slowly distilled OH? and the mixture isthen refluxed for 8 hours (inner temperature 120). The mixture is pouredinto 600 parts by volume of water and the solution is extracted 5 timeswith 80 parts by volume of ether each time. The combined ether extractsare washed twice with 20 parts by volume of saturated sodium chloridesolution each time and then dried over sodium sulphate. After removal ofthe ether, 18.3 parts of the oily amine are obtained by distillation at8284/ 12 torr. As the distillate still contains diethylene glycolmonomethyl ether, it is purified as follows: 221 parts of crude amineare dissolved in 1500 parts by volume of dry ether and hydrogen chlorideis introduced into the solution at 0 until no more hydrochlorideprecipitates. The octahydro 1,2,4 methenopentalenyl (5) aminehydrochloride so isolated is washed with ether and dried in vacuo. Itmelts at 265270.

(c) 117 parts of the above amine hydrochloride are dissolved in parts byvolume of water and the solution is shaken with 200 parts by volume of 4N sodium hydroxide solution. The precipitated amine is extracted 4 timeswith 150 parts by volume of ether each time and the ethereal solution isdried with sodium sulphate. After removal of the ether and distillation,the amine is obtained as a colourless liquid. Theoctahydro-1,2,4-methenopental-' enyl-(5)-amine boils at 81-83/12 torr n1.5160.

(d) 6.45 parts of dimethyl carbamic acid chloride are added dropwise toa solution of 8.1 parts of octahydro- 1,2,4-methenopentalenyl-(5)-amineand 6.3 parts of triethylamine in 80 parts by volume of benzene, theaddition being made at a temperature of 5-l0. The reaction mixture isthen stirred for another 2 hours at 25. The precipitated triethylaminehydrochloride is filtered off and the solution is washed with water.After drying, the henzene is removed in a rotary evaporator. TheN-octahydro 1,2,4 methenopentalenyl (5) N',N dimethyl urea obtained issublimed at 150/ 1 torr and melts at 138- 140.

EXAMPLE 3 16.1 parts of octahydro-1,2,4-methenopentalenyl-(5)-isocyanate (cf. Example 1(b)) are dissolved in 200 parts by volume ofbenzene and 7 parts of methoxy-methylamine are added dropwise within 12minutes in such a way that the temperature does not rise above 5. TheWhole is stirred for 20 minutes at 25 and then the solvent is removed invacuo. The residue is distilled and an oil, boiling at 112-114/ 0.07torr, is obtained which slowly solidifies. TheN-octahydro-1,2,4-methenopentalenyl- (5)-N-methyl-N'-methoxy urea meltsat 73-76.

EXAMPLE 4 8.05 parts of octahydro-1,2,4-methenopentalenyl-(5)-isocyanate (cf. Example 1(b)) are dissolved in 50 parts by volume oftetrahydrofuran and ammonia is introduced into this solution whilestirring. The reaction mixture is stirred at room temperature foranother 45 minutes and then the solvent is evaporated in vacuo. TheN-octahydro- 1,2,4 methenopentalenyl (5)-urea which remains melts at140.

EXAMPLE 5 13.5 parts of octahydro 1,2,4-methenopentalenyl-(5) amine aredissolved in 200 parts of benzene and the solution is added dropwisewithin 30 minutes to 11.8 parts of phenyl isocyanate in 100 parts ofbenzene, the addition being made at 20-30 while cooling with an icebath. The reaction mixture is then stirred for 16 hours at 50- 60whereupon it is filtered and the residue is recrystallised from ethylacetate. The N-octahydro-1,2,4-methenopentalenyl-()-N-phenyl ureaobtained melts at l8l182.

EXAMPLE 6 Example 1 is repeated but in lieu of the octahydro- 1,2,4methenopentalenyl (5 carboxylic acid produced as described by Hall,supra, there is used the same acid produced by saponification from itsethyl ester, obtained by the process of Schrauzer et al. [Chem. Berichte97, 2451 (1964)].

For this purpose, 288 g. of ethyloctahydro-1,2,4-methenopentalenyl-(S)-carboxylate are dissolved in amixture of 75 g. of sodium hydroxide, 850 ml. of water and 250 ml. ofethanol, and the whole is boiled under reflux for 6 hours. The solutionis then concentrated to a volume of 600 ml., and acidified with 250 ml.of concentrated hydrochloric acid. An oil layer forms which is separatedfrom the aqueous phase and then mixed with 500 ml. of diethyl ether. Theaqueous phase is extracted twice with with each time 100 ml. of diethylether. The combined ether solutions are then washed with water and driedover anhydrous sodium sulfate. The ether solvent is then evaporated andthe residue distilled under vacuum. The fraction boiling at l03-105under 0.3 torr is the freeoctahydro-1,2,4-methenopentalenyl-(5)-carboxylic acid. It is obtained inan amount of 199.1 g. (82% yield rate).

When using this acid as starting material in Example 1 and otherwiserepeating the entire procedure of that example, there is obtainedN-octahydro 1,2,4-methenopentalenyl-(S)-N,N'-diethyl urea (melting point88-89 having the excellent herbicidal properties described hereinbefore.

Besides the already mentioned ureas those listed in the following tableare similarly useful and are also obtained by the process described inExamples 1 and 6 when equivalent amounts of the corresponding startingmaterials are used:

heated in a steam bath for minutes. Acetic acid is then added until themixture is neutral and all volatile products are removed by evaporation.The residue is shaken with 100 parts by volume of water. The water isdecanted. 250 parts by volume of petroleum ether are added to theinsoluble residue, the whole is left to stand for some hours and thenfiltered. The filtrate is concentrated, and the oily residue isdistilled. It boils at 97l0l/0.02 torr. Theoctahydro-1,2,4-methenopentalenyl-(5 -carbamic acid methyl estercrystallises and, after recrystallisation from petroleum ether, melts at84-86.

29 parts of this carbam-ic acid methyl ester and 42 parts of potassiumhydroxide are boiled in parts by volume of water and 200 parts by volumeof diethylene glycol monomethyl ether as solvent. 35 parts by volume ofWater are slowly distilled off; the solution finally boils at 125. It isthen boiled for 8 hours. The mixture is poured into 600 parts by volumeof Water and the solution is extracted 5 times with parts by volume ofether each time. The ether extracts are combined and washed twice with20 parts by volume of saturated sodium chloride solution each time andthen dried over sodium sulphate. After removal of the ether,distillation at 82-84/ 12 torr yields 18.3 parts of oily amine. Thisamine still contains diethylene glycol monomethyl ether as impurity andis purified by way of the hydrochloride as described in Example 2(b) and2(c). It is then further reacted as described in step (d) of Example 2,and N-octahydro-l,2,4-methenopentalenyl-(S -N,N-dimethy1 urea of theherbicidal properties described hereirrbefore is obtained.

The herbicidal compositions according to the invention are produced inthe known way by intimately mixing and milling active substances ofgeneral Formula I with suitable carriers, optionally with the additionof dispersing agents or solvents which are inert to the activesubstances. The active substances can be present and used in dusts,sprinkling agents, granulates, coated granules, impregnatedN-octahydro-l,2,4-methenopentalenyl-(5)-N-cycl0propyl ureaN-octahydro-1,2,4-methen0pentalenyl-(5)N-cyclobutyl urea-N-octahydro-1,2,4-methenopentalenyl-(5)-N -cyclopentyl ureaN-octahydro-l,2,4-methenopentalonyl- (5) -N'-eyclohexyl urea 220-225N-octahydro-l,2.4-Inethenopentalenyl-(5)-urea 140-145N-octaliydro-l,2,4-methenopentalenyl-(5)-N-n1ethyl urea 116-118N-octahydro-l,2,4-methenopentalenyl-(5)-N, N-dimethyl uroa 128-130N-octahydro-I ,2,4-rnethenopentalenyl-(5) -N-tetramethylene urea.169-170 N-octaliydro-l ,2,4-methenopentalenyl-(5)-N N -diethyl urea86-88 N-octahydro-l,2,4-methenopentalenyl-(5)-N -pentamethylene urea-166-168 N -octal1ydr0-1,2,4-methenopentalenyl-(5) -N ethyleneoxyethylene173-175 urea. 24 N-octahydro-l,2,4-methenopentalenyl-(5)-N-methyl-N -(1--107 metl1yl-2-propinyl)-urca. 25N-octahydro-l,2,4-methen0pentalenyl-(5)-N-methyl-N- 2 109-112 methoxyurea.

1 0.04 torr. 2 0.06 torr.

EXAMPLE 26 60 granules, homogeneous granules; wettable powders, pastes,

10 parts of octahydro 1,2,4 methenopentalenyl-(5)- carboxylic acid ethylester, 40 parts by volume of a 26% by volume aqueous ammonia solutionand 5 parts by volume of methanol are heated in an autoclave for 10hours at Volatile parts are removed from the reaction product by waterjet vacuum. 25 parts by volume of the acetone are added to the residue,the mixture is filtered and the residue is recrystallised from water.The octahydro-1,2,4-methenopentalenyl-(5) carboxylic acid amide obtainedmelts at l60l69 (with decomposition).

16.3 parts of octahydro-1,2,4-methenopentalenyl-(5)- carboxylic acidamide are dissolved in 500 parts by volume 0| methanol. 1 1 parts ofsodium methylate are then added and the whole is left to stand for 30minutes and then emulsions; solutions and aerosols.

The concentration of active substance in these compositions is, e.g.,0.01 to 80%.

Other biocidal active substances or agents can be admixed with thecompositions according to the invention. Thus, the new compositions, inaddition to the compounds mentioned of general Formula I can contain,e.g., insecticides, other herbicides, fungicides, bactericides,fungistatica, bacteriostatica or nematocides, to widen the range ofaction.

As herbicides can be mentioned, for instance, halogendiamino,alkoxy-diaminoand alkylthio-diamino-s-triazines, in particular,2-chloro-4-methylamino-6-isopropylamino-s-triazine, 2chloro-4,6-diethylamino-s-triazine, 2- chloro 4 ethylamino 6isopropylamino-s-triazine, 2-

.pylaminoMs-triazine, Z-methoxy 4,6bis-(3'-rnethoxypropylamino)-s-triazine and 2-methylthio 4,6 bis-(3-methoxypropylamino -s-triazine.

The compositions according to the invention can also contain syntheticfertilisers and trace elements.

The following examples serve to illustrate the application part of thepresent invention; where not otherwise stated, parts mean parts byweight.

WE'IT-ABLE POWDER The following components are used to product a 50%Wettable powder:

50 parts of octahydro-1,2,4-methenopentalenyl-(5)-N',N-

dimethyl urea,

5 parts of dibutylphenyl/ ethylene oxide condensate,

5 parts ofa naphthalene sulphonic acid/phenol sulphonic acid/formaldehyde condensation product,

40 parts of Champa-gen chalk.

The active substances mentioned are drawn onto the carriers and thenmixed and milled with the additives given. Wettable powders havingexcellent wettability and suspendibility are obtained. Suspensions ofany concentration desired can be obtained from such Wettable powders bydilution with water.

GRANULATE '90 parts of a granular carrier, e.g., sand, kaolin,montmorillonite, are moistened with 1.5 parts of water, isopropanel orpolyethylene glycol and mixed with parts of N-octahydro 1,2,4methenopentalenyl-(S)-N-methyl urea.

These compositions are applied preferably in such amounts that at leastabout 0.5 kg., but not more than 5 kg. of active ingredient are appliedper hectare of area in which the growth of weeds and undesirable grassesis to be controlled.

10 We claim: 1. A compound of the formula wherein R represents hydrogen,alkyl of from 1 to 5 carbon atoms,

alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms,cycloalkyl of from 3 to 8 carbon atoms, or phenyl, and

R represents hydrogen, alkyl of from 1 to 4 carbon atoms,

or alkenyl of 3 or 4 carbon atoms.

2. A compound as defined in claim 1, which isN-octahydro-1,2,4-methenopenta1enyl-(5) -N-methyl urea.

3. A compound as defined in claim 1, which isN-octahydro-1,2,4-methenopentalenyl- (5 )-N',N'-dimethyl urea.

4. A compound as defined in claim 1, which isN-octahydro-1,2,4-methenopentalenyl-(5) -N',N'-diethyl urea.

5. A compound as defined in claim 1, which isN-octahydro-1,2,4-methenopentalenyl (5) N-(1'-methyl-2'- propinyl)-N-methyl urea.

References Cited UNITED STATES PATENTS 3,163,674 12/1964 Buntin 2605533,174,843 3/1965 Buntin et a1. 260533X 3,276,855 10/1966 Richter 260453X3,304,167 2/1967 Buntin et al. 260553X 3,332,975 7/1967 Bauer et a1.260453 3,347,658 10/1967 Luckenbaugh 260553X 3,365,289 l/l968 Raff etal. 260553X 3,395,233 7/1968 Duerr et al. 260453X FOREIGN PATENTS1,479,858 3/ 1967 France 260553 1,481,308 4/1967 France 260553 1,086,52710/ 1967 Great Britain 260553 BERNARD HELFIN, Primary Examiner M. W.GLYNN, Assistant Examiner US. Cl. XJR.

